CN107845804B - Silicon-tin composite negative electrode material of lithium ion battery and preparation method - Google Patents
Silicon-tin composite negative electrode material of lithium ion battery and preparation method Download PDFInfo
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- CN107845804B CN107845804B CN201610832963.7A CN201610832963A CN107845804B CN 107845804 B CN107845804 B CN 107845804B CN 201610832963 A CN201610832963 A CN 201610832963A CN 107845804 B CN107845804 B CN 107845804B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery silicon-tin composite cathode material and a preparation method thereof, wherein the lithium ion battery silicon-tin composite cathode material consists of a micron-sized silicon material and tin which is uniformly chemically plated on the surface of the silicon material, wherein the weight percentage content of element silicon is 20-75%, and the weight percentage content of element tin is 25-80%, and the micron-sized silicon material is placed in a chemical plating solution and continuously stirred so as to be uniformly dispersed in the chemical plating solution in the chemical plating process; the chemical plating temperature is 50-80 ℃, and the chemical plating time is 2-10 min. Sensitization and activation are not needed in the chemical plating process, so that the cost is reduced and the process is simplified; after the silicon cathode material is modified by chemical tinning, the capacity and the electrochemical performance of the silicon cathode material are improved. The prepared silicon-tin alloy lithium ion battery cathode material has high specific capacity and stable cycle performance, and can still keep more than 500mAh/g after 10 times of cycle.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a silicon-tin alloy cathode material of a lithium ion battery and a preparation method thereof.
Background
In recent years, lithium ion batteries have been developed rapidly, have the advantages of high voltage, high energy density, good cycle performance, small self-discharge, no memory effect and the like, have been developed rapidly in recent 10 years, and have been widely applied in the field of mobile electronic terminal devices such as mobile phones, notebook computers, mobile phones, armed devices, camcorders and the like due to the advantage of excellent high cost performance. Most of the current commercialized lithium ion battery negative electrode materials adopt carbon materials, and although the materials have excellent electrochemical performance, the lithium storage capacity is low. The actual specific capacity of the high-capacity chemical power supply is very close to the theoretical specific capacity at present, and the potential for further developing the specific capacity is very small, so that the high-capacity chemical power supply is difficult to adapt to the wide requirements of the development of electric automobiles and other high-power equipment on high-capacity high-power chemical power supplies. Therefore, research and development of a novel lithium ion battery anode material with high specific capacity becomes a current research hotspot.
The inorganic non-metallic silicon has good lithium storage performance and forms Li4.4When the Si alloy is used, the theoretical specific mass capacity is 4200mAh/g, so that the Si alloy is a promising negative electrode material and is widely concerned all over the world. However, the silicon material will expand in volume during lithium intercalation and deintercalation400%, the main material will be broken, pulverized and fall off from the current collector, and in addition, the conductivity of silicon is not good, and the conductivity is only 6.7 × 10-4S cm-1Therefore, the silicon material alone cannot be used as the negative electrode material of the lithium ion battery. The silicon-based alloy adopts an active/inactive or active/active structure, and can effectively inhibit the expansion of the electrode due to the buffering action of other elements when lithium is inserted and removed, thereby improving the conductivity and finally prolonging the cycle life of the electrode. Therefore, the silicon-based alloy becomes a research hotspot of the current lithium ion battery cathode material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a silicon-tin composite cathode material of a lithium ion battery and a preparation method thereof, which can improve the reversible capacity of the cathode material of the lithium ion battery and improve the electrochemical performance of the cathode material of the lithium ion battery.
The technical purpose of the invention is realized by the following technical scheme:
a silicon-tin composite cathode material of a lithium ion battery and a preparation method thereof are disclosed, which comprises a micron-sized silicon material and tin uniformly chemically plated on the surface of the silicon material, wherein the weight percentage content of element silicon is 20-75%, the weight percentage content of element tin is 25-80%, the weight percentage content of preferred element silicon is 21.6-73.9%, the weight percentage content of element tin is 26.1-78.4%, the weight percentage content of more preferred element silicon is 25-55%, and the weight percentage content of element tin is 45-75%.
The micron-sized silicon material is powder material with the grain diameter of 1-5 mu m.
The method comprises the following steps: placing the micron-sized silicon material in chemical plating solution and continuously stirring to uniformly disperse the micron-sized silicon material in the chemical plating solution in the chemical plating process, wherein the chemical plating solution is aqueous solution, and SnCl2·2H2The concentration of O is 70-80 g/L, the concentration of NaOH is 100-120 g/L, and the concentration of sodium citrate is 200-250 g/L; chemical plating process parameters: the chemical plating temperature is 50-80 ℃, and the chemical plating time is 2-10 min.
In the above technical scheme, SnCl2·2H2The concentration of O is 75-80 g/L, the concentration of NaOH is 100-110g/L, and the concentration of the sodium citrate is 220-235 g/L.
In the technical scheme, the chemical plating temperature is 60-70 ℃, and the chemical plating time is 5-8 min.
In the technical scheme, the stirring condition is 200-300 revolutions per minute/min.
The invention aims to prepare silicon-tin alloy cathode materials with different proportions by adopting a chemical plating method, and the silicon-tin alloy cathode materials are used for improving the electrochemical performance of the silicon-tin alloy cathode materials. Sensitization and activation are not needed in the chemical plating process, so that the cost is reduced, and the process is simplified; in addition, after the silicon cathode material is modified by chemical tinning, the capacity and the electrochemical performance of the silicon cathode material are improved. The prepared silicon-tin alloy lithium ion battery cathode material has high specific capacity and stable cycle performance, and can still keep more than 500mAh/g after 10 times of cycle.
Drawings
FIG. 1 is a scanning electron microscope image of the silicon-tin composite material in example 1.
Fig. 2 is an X-ray diffraction picture of the silicon-tin composite material in example 1.
FIG. 3 is a charge-discharge life curve of the silicon-tin composite material in example 1.
FIG. 4 is a scanning electron microscope image of the silicon-tin composite material in example 2.
Fig. 5 is an X-ray diffraction picture of the silicon-tin composite material in example 2.
FIG. 6 is a charge-discharge life curve of the silicon-tin composite material in example 2.
FIG. 7 is a scanning electron micrograph of the silicon-tin composite material of example 3.
Fig. 8 is an X-ray diffraction picture of the silicon-tin composite material in example 3.
FIG. 9 is a charge-discharge life curve of the silicon-tin composite material in example 3.
FIG. 10 is a SEM image of the Si-Sn composite material of example 4.
Fig. 11 is an X-ray diffraction picture of the silicon-tin composite material in example 4.
FIG. 12 is a charge-discharge life curve of the silicon-tin composite material in example 4.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples. The particle size of the raw material silicon powder is 1-4 μm, the raw material silicon powder is purchased from Alfa aesar, and Si powder is cleaned and dried by acetone ethanol and the like for later use before chemical plating Sn; SnCl2·2H2O, NaOH sodium citrate is from Tianjin Yuanli chemical Co Ltd; the model of a scanning electron microscope of the tester is Hitachi S-4800, the model of an X-ray diffractometer is Japan science D/MAX-2500, and the model of a charging and discharging tester is Wuhan LAND.
Example 1
Preparing a plating solution: SnCl275g/L, NaOH100g/L and sodium citrate 233 g/L;
chemical plating time: 5min
Chemical plating temperature: 50 deg.C
Stirring conditions are as follows: 300 revolutions per minute/min
And (3) post-processing: cleaning and filtering a product subjected to chemical plating by using deionized water, and then putting the product into a blast oven for drying to obtain a silicon-tin composite material, wherein the silicon content in the material is 73.9%, and the tin content in the material is 26.1%; the material is taken as a negative electrode material to assemble a button cell, the conductive agent is acetylene black, and the binder is PVDF; the mass ratio of the silicon-tin active substance to the conductive agent to the binder is 70:15: 15; the charge-discharge current density was 100 mA/g.
FIG. 1 is an SEM photograph of a silicon-tin composite material in example 1 (scanning electron microscope model: Hitachi S-4800)
FIG. 2 is an XRD pattern of silicon in example 1, and it can be confirmed that Si and Sn are present in the material (X-ray diffractometer model: Japanese science D/MAX-2500)
FIG. 3 is a charge/discharge life curve of the Si-Sn composite material of example 1, in which the first discharge capacity is 2431.3mAh/g, and the specific discharge capacity after 10 cycles is maintained at 546.7mAh/g (type of charge/discharge tester: Land, Wuhan)
Example 2
Preparing a plating solution: SnCl270g/L, NaOH120g/L and sodium citrate 200 g/L;
chemical plating time: 8min
Chemical plating temperature: 80 deg.C
Stirring conditions are as follows: 200 revolutions per minute/min
And (3) post-processing: cleaning and filtering a product subjected to chemical plating by using deionized water, and then putting the product into a blast oven for drying to obtain a silicon-tin composite material, wherein the silicon content in the material is 55%, and the tin content in the material is 45%; the material is taken as a negative electrode material to assemble a button cell, the conductive agent is acetylene black, and the binder is PVDF; the mass ratio of the silicon-tin active substance to the conductive agent to the binder is 70:15: 15; the charge-discharge current density was 100 mA/g.
FIG. 4 is an SEM photograph of the SiSn composite material in example 2 (scanning electron microscope model: Hitachi S-4800)
FIG. 5 is an XRD pattern of silicon in example 2, and it can be confirmed that Si and Sn are present in the material (X-ray diffractometer model: Japanese science D/MAX-2500)
FIG. 6 is a charge/discharge life curve of the Si-Sn composite material of example 2, in which the first specific discharge capacity is 2620.1mAh/g, and the specific discharge capacity after 10 cycles is maintained at 500.6mAh/g (type of charge/discharge tester: Land, Wuhan)
Example 3
Preparing a plating solution: SnCl275g/L, 110g/L NaOH and 220g/L sodium citrate;
chemical plating time: 2min
Chemical plating temperature: 75 deg.C
And (3) post-processing: cleaning and filtering a product subjected to chemical plating by using deionized water, and then putting the product into a blast oven for drying to obtain a silicon-tin composite material, wherein the silicon content in the material is 52.6%, and the tin content in the material is 47.4%; the material is taken as a negative electrode material to assemble a button cell, the conductive agent is acetylene black, and the binder is PVDF; the mass ratio of the silicon-tin active substance to the conductive agent to the binder is 70:15: 15; the charge-discharge current density was 100 mA/g.
FIG. 7 is an SEM photograph of a silicon-tin composite material in example 3 (scanning electron microscope model: Hitachi S-4800)
FIG. 8 is an XRD pattern of silicon in example 3, and it can be confirmed that Si and Sn are present in the material (X-ray diffractometer model: Japanese science D/MAX-2500)
FIG. 9 is a charge/discharge life curve of the Si-Sn composite material in example 3, in which the first specific discharge capacity is 2155.9mAh/g, and the specific discharge capacity after 10 cycles is kept at 549.8mAh/g (type of charge/discharge tester: Land, Wuhan)
Example 4
Preparing a plating solution: SnCl275g/L, 100g/L NaOH and 250g/L sodium citrate;
chemical plating time: for 10min
Chemical plating temperature: 60 deg.C
And (3) post-processing: cleaning and filtering a product subjected to chemical plating by using deionized water, and then putting the product into a blast oven for drying to obtain a silicon-tin composite material, wherein the silicon content in the material is 39.2%, and the tin content in the material is 60.8%; (ii) a The material is taken as a negative electrode material to assemble a button cell, the conductive agent is acetylene black, and the binder is PVDF; the mass ratio of the silicon-tin active substance to the conductive agent to the binder is 70:15: 15; the charge-discharge current density was 100 mA/g.
FIG. 10 is an SEM photograph of the SiSn composite material in example 4 (scanning electron microscope model: Hitachi S-4800)
FIG. 11 is an XRD pattern of silicon in example 4, and it can be confirmed that Si and Sn are present in the material (X-ray diffractometer model: Japanese science D/MAX-2500)
FIG. 12 is a charge/discharge life curve of the Si-Sn composite material of example 4, in which the first specific discharge capacity is 1897.6mAh/g, and the specific discharge capacity after 10 cycles is maintained at 524.1mAh/g (type of charge/discharge tester: Land, Wuhan)
The silicon-tin composite material can be prepared by adjusting the preparation method according to the process parameters disclosed by the invention, the simple substances of Si and Sn exist in tests, the first discharge specific capacity is 1880-2650 mAh/g, and the discharge specific capacity after 10 cycles is kept above 500 mAh/g.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (9)
1. A silicon-tin composite cathode material of a lithium ion battery,the method is characterized by comprising a micron-sized silicon material and tin uniformly chemically plated on the surface of the silicon material, wherein the weight percentage content of elemental silicon is 20-75%, and the weight percentage content of elemental tin is 25-80%2·2H2The concentration of O is 70-80 g/L, the concentration of NaOH is 100-120 g/L, and the concentration of sodium citrate is 200-250 g/L; chemical plating process parameters: the chemical plating temperature is 50-80 ℃, and the chemical plating time is 2-10 min.
2. The silicon-tin composite anode material for the lithium ion battery as claimed in claim 1, wherein the weight percentage content of the element silicon is 21.6% -73.9%, and the weight percentage content of the element tin is 26.1-78.4%.
3. The silicon-tin composite anode material for the lithium ion battery according to claim 1, wherein the weight percentage of the element silicon is 25-55%, and the weight percentage of the element tin is 45-75%.
4. The silicon-tin composite anode material for the lithium ion battery as claimed in any one of claims 1 to 3, wherein the micron-sized silicon material is a powder material with a particle size of 1 to 5 μm.
5. A preparation method of a silicon-tin composite negative electrode material of a lithium ion battery is characterized in that micron-sized silicon materials are placed in chemical plating solution and continuously stirred so that the micron-sized silicon materials are uniformly dispersed in the chemical plating solution in the chemical plating process, the chemical plating solution is aqueous solution, and SnCl is used as the aqueous solution2·2H2The concentration of O is 70-80 g/L, the concentration of NaOH is 100-120 g/L, and the concentration of sodium citrate is 200-250 g/L; chemical plating process parameters: the chemical plating temperature is 50-80 ℃, and the chemical plating time is 2-10 min; the lithium ion battery silicon-tin composite negative electrode material consists of micron-sized silicon material and tin uniformly chemically plated on the surface of the silicon material, wherein the element siliconThe content of the element tin is 20 to 75 percent by weight, and the content of the element tin is 25 to 80 percent by weight.
6. The preparation method of the silicon-tin composite anode material for the lithium ion battery according to claim 5, wherein the SnCl is2·2H2The concentration of O is 75-80 g/L, the concentration of NaOH is 100-110 g/L, and the concentration of sodium citrate is 220-235 g/L.
7. The preparation method of the silicon-tin composite negative electrode material of the lithium ion battery according to claim 5, wherein the chemical plating temperature is 60-70 ℃, and the chemical plating time is 5-8 min.
8. The preparation method of the silicon-tin composite anode material for the lithium ion battery as claimed in claim 5, wherein the stirring condition is 200-300 revolutions per minute.
9. The use of the silicon-tin composite negative electrode material for lithium ion batteries according to any of claims 1 to 3 in the field of batteries, characterized in that the specific capacity is maintained at more than 500mAh/g after 10 cycles.
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| CN101071851A (en) * | 2007-06-13 | 2007-11-14 | 天津大学 | Tin-cobalt alloy negative electrode material for lithium ion cell and its preparing method |
| CN101192667A (en) * | 2006-11-27 | 2008-06-04 | 三星Sdi株式会社 | Negative active material and rechargeable lithium battery including the same |
| CN102400119A (en) * | 2010-09-15 | 2012-04-04 | 吉林师范大学 | Chemical nickel plating method on magnesium alloy |
| CN104701514A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Lithium ion battery anode material, preparation method thereof and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101192667A (en) * | 2006-11-27 | 2008-06-04 | 三星Sdi株式会社 | Negative active material and rechargeable lithium battery including the same |
| CN101071851A (en) * | 2007-06-13 | 2007-11-14 | 天津大学 | Tin-cobalt alloy negative electrode material for lithium ion cell and its preparing method |
| CN102400119A (en) * | 2010-09-15 | 2012-04-04 | 吉林师范大学 | Chemical nickel plating method on magnesium alloy |
| CN104701514A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Lithium ion battery anode material, preparation method thereof and lithium ion battery |
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| 利用歧化反应法化学镀锡;钟小芳 等;《湘潭大学自然科学学报》;19980630(第2期);第66-69页 * |
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